WO2000057507A1 - Electrodes - Google Patents
Electrodes Download PDFInfo
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- WO2000057507A1 WO2000057507A1 PCT/AU2000/000241 AU0000241W WO0057507A1 WO 2000057507 A1 WO2000057507 A1 WO 2000057507A1 AU 0000241 W AU0000241 W AU 0000241W WO 0057507 A1 WO0057507 A1 WO 0057507A1
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- WIPO (PCT)
- Prior art keywords
- electrode
- layer
- substrate material
- electrochemically active
- active material
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/42—Grouping of primary cells into batteries
- H01M6/46—Grouping of primary cells into batteries of flat cells
- H01M6/48—Grouping of primary cells into batteries of flat cells with bipolar electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49112—Electric battery cell making including laminating of indefinite length material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Definitions
- Electrodes are commercially applied in a wide variety of applications including being used in redox flow cells, in battery stacks and other electrochemical applications such as electrodepositing and electrowinning.
- Polymer composites or conducting plastic composites generally comprise polymer mixed with one or more forms of carbon and/or graphite and then pressure moulded to form the electrode.
- silver or aluminium particles can be added to ordinary polymers.
- composite plastic electrode materials which have been used as bipolar and end electrodes in fuel cell and redox battery cell applications include cross-linked polymer composite electrodes containing carbon black, a carbon fibre-carbon black thermosetting resin composite bipolar electrode, carbon-fibre -mat/resin electrode materials, carbon plastic electrodes based on
- WO 94/06164 discloses a conducting plastic composite electrode comprising a thermoplastic polymer, an elastomeric polymer and a conductive filler.
- the polymer/polymer blend is mixed with the chosen form of carbon/graphite at moderately high temperature ( > 100°C) and then heat and pressure moulded to form a thin, smooth conducting plastic composite sheet with good electrical conductivity and therefore low resistivity.
- an end-electrode for a redox battery is made.
- a bipolar electrode for a redox battery is completed.
- a window having a border typically of about l-8cm around the electrode edges
- a composite containing 70% HDPE, 15 % carbon black and 15 % graphite fibre obtained by the conventional mixing and compression moulding process has been shown to have a resistivity of around 1 ohm/cm.
- Bipolar electrodes of the composites obtained from the new SIC method described above have overall area resistivities of 0.4-2.0 ohms. cm 2 .
- some of the thin composite plastic sheets used in electrodes may have a high permeability due to pinholes and voids which, when used in redox flow cells, results in the electrolyte passing through the
- the bipolar electrode should also be cheap to manufacture, of negligible permeability, electrochemically active and stable in the electrolyte during charge-discharge cycling of a battery. It should also avoid delaminating during overcharging conditions.
- an electrode particularly an end electrode, which has low resistivity and therefore high conductivity, which is strong even when used in the 5 standard millimetre or less thicknesses and which can be used in a stack assembly without the need for insulating edging or other precautionary measures and which does not present or cause current bypass or current leakage in such stacks.
- the end electrode should also be cheap to manufacture and of negligible permeability.
- 'non conductive' is defined to mean having a resistivity higher than lOOO ⁇ cm.
- electrode' is defined to include a bipolar electrode and an end electrode. 25 Where the terms 'comprise' , 'comprises' , 'comprised' or 'comprising' are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one of more other features, integers, steps, components or groups thereof.
- the present inventors have now discovered that it is possible to form an electrode, particularly a bipolar electrode, having a non-conductive electrode substrate material which simplifies battery stack assembly and flow-frame design.
- the resulting bipolar electrode has good mechanical properties, high electrochemical activity and good conductivity which is as high or higher than that obtained using
- a first aspect of the present invention provides an electrode including a layer of non-conductive electrode substrate material having a first surface and a second surface, one of said first and second surfaces carrying a first layer of electrochemically active material, the other of said surfaces carrying a second layer of either electrochemically active material or electrically conductive material and wherein said first and second layers contact so as to provide a current transfer pathway through said substrate material.
- a first embodiment of the first aspect of the present invention provides a bipolar electrode including a layer of non-conductive plastic electrode substrate material having a first surface and a second surface, each of said first and second surfaces carrying a layer of electrochemically active material wherein said layers of electrochemically active material contact so as to provide a current transfer pathway through said ⁇ o substrate material.
- a second embodiment of the first aspect of the present invention provides a bipolar electrode including a layer of non-conductive polymeric electrode substrate material having a first surface and a second surface, each of said first and second surfaces carrying a layer of electrochemically active material wherein said layers of i s electrochemically active material contact so as to provide a current transfer pathway through said polymeric substrate material.
- a third embodiment of the first aspect of the present invention provides a bipolar electrode including a layer of non-conductive polymeric electrode substrate material having a first surface and a second surface, each of said first and second surfaces
- melt flow index MFI
- 5 190°C/2.16kg
- bipolar electrode including a layer of non-conductive polymeric electrode substrate material having a first surface and an opposing second surface, each of said first and second surfaces carrying a layer of electrochemically active material and wherein said polymeric material is characterised by a melt flow index (MFI) which enables at least one of the opposing layers of electrochemically active material to penetrate through said MFI
- melt flow index MFI
- each of said first and second surfaces carrying a layer of electrochemically active material such that said bipolar electrode has an area resistivity of less than 2 ⁇ cm 2 in a direction perpendicular to the first or second surface.
- a seventh embodiment of the first aspect of the present invention provides an electrode including a layer of non-conductive plastic electrode substrate material having ⁇ o a first surface and a second surface, each of said first and second surfaces carrying a layer of electrochemically active material such that said electrode has through conductivity with an area resistivity of less than 2 ⁇ cm 2 in a direction perpendicular to the first or second surface.
- electrode including a layer of non-conductive plastic electrode substrate material having a first surface and a second surface, each of said first and second surfaces carrying a layer of electrochemically active material and wherein said layers of electrochemically active material contact so as to provide a current transfer pathway through said polymeric material such that said electrode has an area resistivity of less than 2 ⁇ cm 2 in
- a ninth embodiment of the first aspect of the present invention provides an end electrode including a layer of non-conductive plastic electrode substrate material having a first surface and a second surface, one of said first and second surfaces carrying a first layer of electrochemically active material, the other of said surfaces carrying a
- substrate material is a non-conductive polymeric material characterised by a melt flow index (MFI) of greater than 5 (190°C/2.16kg) [g/lOmin] such that the first and second layers contact so as to provide a current transfer pathway through said polymeric substrate material.
- MFI melt flow index
- non- conductive plastic electrode substrate material is a non-conductive polymeric material characterised by a melt flow index (MFI) which enables the layer of electrochemically active material to penetrate through said polymeric substrate material and contact the electrically conductive material so as to provide a current transfer pathway through said polymeric substrate material.
- MFI melt flow index
- a twelfth embodiment of the first aspect of the present invention provides an end electrode including a layer of non-conductive plastic electrode substrate material having 5 a first surface and a second surface, one of said first and second surfaces carrying a layer of electrochemically active material, the other of said surfaces carrying a second layer of electrically conductive material such that said electrode has an area resistivity of less than 2 ⁇ cm 2 in a direction perpendicular to the first or second surface.
- a thirteenth embodiment of the first aspect of the present invention provides an ⁇ o end electrode including a layer of non-conductive plastic electrode substrate material having a first surface and a second surface, one of said first and second surfaces carrying a first layer of electrochemically active material, the other of said surfaces carrying a second layer of electrically conductive material such that said electrode has through conductivity with an area resistivity of less than 2 ⁇ cm 2 in a direction i s perpendicular to the first or second surface.
- a fourteenth embodiment of the first aspect of the present invention provides an electrode including a layer of non-conductive plastic electrode substrate material having a first surface and a second surface, one of said first and second surfaces carrying a first layer of electrochemically active material, the other of said surfaces carrying a 2o second layer of electrically conductive material wherein said first and second layers contact such that said electrode has through conductivity with an area resistivity of less than 2 ⁇ cm 2 in a direction perpendicular to the first or second surface.
- said layer of electrically conductive material acts as a current collector.
- an end electrode for use in a bipolar stack including a layer of non-conductive polymeric electrode substrate material having a first surface and an opposing second surface, one of said first and second surfaces
- a bipolar electrode including a layer of non-conductive polymeric electrode substrate material having a first surface and an opposing second surface, each of said first and second surfaces having bonded to them, a layer of graphite or carbon felt and wherein said polymeric material is characterised by a MFI such that graphite or carbon fibres of said
- a bipolar electrode of the present invention further includes a layer of electrically conductive material contacting one of the first or second layers of electrochemically active material
- the layer of electrically conductive material acts as a current collector.
- the first and second surfaces of the sheet of substrate material are opposing as in opposing facing.
- the layer of substrate material is in the form of a thin sheet or strip.
- the non-conductive electrode substrate material is plastic, as fibrous electrochemically active material is more easily able to penetrate through such a material. It is therefore typical in the bipolar electrodes of the present invention that the electrode substrate material is plastic as the fibres from each of the opposing layers of fibrous electrochemically active material can penetrate and contact through such a material. More typically, the electrode substrate material is a polymeric material. Typically, any insulating polymeric material can be used.
- polymers examples include, by way of illustration only, endcapped polyacetals such as poly(oxymethylene), poly formaldehyde,
- the polymer is characterised by a melt flow index (MFI) which allows the penetration of the opposing layers of electrochemically active material into the polymer material during formation of the bipolar electrode such that the opposing layers
- MFI melt flow index
- the MFI of the polymer used in the formation of the electrodes of the present invention measured at 190°C under a 2.16kg load according to ASTM D1238, is typically in the range of from 5-70 (190°C/2.16kg([g/10minJ, also typically in the range of from 5-50 (190°C/2.16kg([g/10min] , more typically in the range of from 10-40 ( 190°C/2.16kg([g/10min] , even more typically in the range of from 10-20 ( 190°C/2.16kg([g/10min] still more typically in the range of from 10-15 ( 190°C/2.16 g([g/10min] .
- the temperature and pressure required for the bonding process depends on the melting point and melt flow index of the polymeric material used. Typically, the higher the melt flow index, the lower the pressure needed to achieve good penetration of the fibres of the layers of ⁇ o electrochemically active material. Typically, the temperature ranges from just above the softening point of the plastic to just below the decomposition temperature.
- a polymeric material having an MFI of about 5 (190°C/2.16kg([g/10min], requires pressure in the range of from 0.1-50kg cm "2 in the felt bonding process.
- the polymeric substrate material is high density polyethylene with an
- MFI 190/2.166 [g/ 10 min] of about 10-17.5.
- Melt flow indices MFI are determined using a melt flow indexer, and in the present case (as stated above) were measured at 190°C under a 2.16kg load.
- the electrochemically active material which is carried on at least one of the opposing surfaces or faces of the electrode substrate material in electrodes of the
- 25 present invention is carbon, graphite, metallized fibres, pitch derived carbon fibres, graphite fibres, poly aery lonitrile carbon fibres and polyacrylocitrile-derived graphite fibres.
- said metal mesh is at least about 0.5mm thick.
- the fibres are woven by conventional weaving machines yielding large fabrics which may be cut into the desired dimensions for the electrode.
- Each electrode may employ a plurality of layers of the material, so that the final dimensions of the electrode may vary widely.
- ⁇ o It is also desirable for the fibres to have a three dimensional structure with at least
- the graphite felt is i s Toyoba. Sigri or FMI carbon or graphite felt types.
- the electrochemically active material which is bonded to each surface of the electrode substrate material in bipolar electrodes of the present invention is about 6mm thick or less.
- Graphite felt which is most commonly used in the preparation of electrodes of the present invention is typically used at a thickness of
- the electrochemically active material is bonded such as by heat and/or compression bonding, onto the opposing surfaces or faces of the electrode substrate material.
- the fibres of the opposing layers of graphite felt or other electrochemically active material are bonded such as by heat and/or compression bonding, onto the opposing surfaces or faces of the electrode substrate material.
- the pressure is
- the mould can be preheated up to 100-750°C, more typically 120-400°C, still more typically 120-220°C (such as for polyethylene or polypropylene).
- Pressure of from about 0.1kg cm -2 up to 5kg cm -2 , typically up to 2-5 kg cm -2 , more typically 2kg cm -2 is applied to the mould at preferably about 120-220°C which is maintained for 5-90 minutes, typically 5-40 minutes, more typically 5-15 minutes.
- the ⁇ o mould is then cooled to room temperature to obtain the bipolar electrode.
- the electrochemically active material such as graphite felt is bonded to the sheet of substrate material at about 110-180°C for LDPE or 130-200°C for HDPE and a pressure in the range of 1 - 20kg cm -2 .
- the bonding typically takes about 5-10 minutes. More typically, the pressure applied is in the range of about l-15kg c ⁇ r 2 , still i s more typically the pressure applied is about 1-lOkg cm -2 .
- the fibres penetrate up to 50- 100% of the thickness of the sheet material, more typically they penetrate up to 50 to 60% of the sheet material from each side.
- the degree of contacting/interconnection of the fibres of the electrochemically active material is responsible for the achieved low
- bipolar electrodes of the present invention provide the alternate current transfer pathway by means of interconnecting of the fibres of the
- the electrodes, particularly the bipolar electrodes of the present invention therefore display good conductivity, excellent mechanical properties and low permeability.
- the properties of the electrodes of the present invention are mainly characterised by the mechanical properties of the polymer which is used as
- the simplicity of the production process offers a drastic reduction of electrode production costs as standard polymer products are used and production time is minimised by avoiding mixing of components or coating procedures, as well as allowing for carbon black dust free cutting of the final design of the electrode.
- the electrodes are extremely cost effective to manufacture and the fact that
- the electrode substrate is non-conductive means that battery stack assembly is now simplified as the application of non-conductive edging to the electrode, or its careful shaping and then alignment in the stack is no longer required. Further, monitoring of individual bipolar cells in a stack (bipolar electrolyser) is also no longer required. Most importantly, now that no carbonaceous forms are required in the substrate
- the electrode does not degrade and no delamination effect is observed during accidental overcharge of the stacks.
- Figure 4 illustrates the assembly of stack components in a vanadium redox cell
- Figure 6 is a graph illustrating the effect of bonding time on conductivity of bipolar electrodes of the present invention.
- a window is placed on either side of the polymer sheet and then an electrochemically active layer, typically a graphite felt layer of dimensions 50 x 50x 2mm, is placed into each of the two windows, and this assembly is then placed in a mould.
- the graphite felt is then heat bonded to both sides in the centre
- FIG. 1 illustrates the assembly with the polymer sheet (1) having a first surface (2) and an opposing second surface (3) which is
- the area resistivity was measured by a method characterised by setting the bipolar electrodes between two copper plates, applying a pressure of 0.2kg cm- 2 .
- the potential was measured by a method characterised by setting the bipolar electrodes between two copper plates, applying a pressure of 0.2kg cm- 2 .
- 35 electrode (700x450x1mm).
- the LDPE sheet is used as a substrate in the above described felt bonding process occurring at about 180°C, with a pressure of about 2.2kg cm "2 being applied to the mould for about 15-30 minutes.
- Felt size was 500x320x5 mm of Sigri Graphite felt.
- HDPE sheets produced by means of compression moulding of HDPE- powder was used for the preparation of carbon black free bipolar graphite felt ⁇ o electrodes.
- the sheets were pressed for 10 minutes in an aluminium mould with the inner mould dimensions of l lOxlOOxlmm (lxwxh) under a pressure of 43kg/cm ⁇ and a temperature of 155 °C.
- the mould was preheated for 10 minutes before applying the pressure. After pressing, the mould was quenched in a cold water tank.
- the physical properties of the i s obtained polymer sheets are given in Table I.
- LDPE sheets produced by means of compression moulding of LDPE- granule was used for the preparation of carbon black free bipolar graphite felt electrodes.
- Alkathene LDPE granule, grade WSM 168, Orica Polythene, Australia was used as granule material.
- the sheets were pressed for 10 minutes in an aluminium 25 mould with the inner mould dimensions of 110 x 100 x 1mm (lxwxh) under a pressure of 43 kg/cm 2 and a temperature of 135°C.
- the mould was preheated for 10 minutes before applying the pressure. After pressing, the mould was quenched in a cold water tank.
- Table 1 The physical properties of the obtained polymer sheets are given in Table 1.
- LDPE sheets produced by means of compression moulding of LDPE- granule was used for the preparation of carbon black free bipolar graphite felt electrodes.
- the sheets were pressed for 10 minutes in an aluminium mould with the inner mould dimensions of 110 x 100 x 1mm (lxwxh) under a pressure
- Table I Mechanical Properties (ASTM D-638) of composite sheets and melt flow index of substrate material (ASTM 1238)
- a preferable design of such a window is a frame which has a special metal lip as it is illustrated in Figure 1 and 2. This lip hinders melted polymer material from creeping up the sidewalls of the graphite felt which can result in an undesirable ridge around the graphite felt making it difficult to seal the electrodes against the electrolyte flow-frames during stack construction.
- the graphite felt sheets (FMI Graphite, USA, 50x50x2 mm) are placed into such windows on both sides of the polymer sheet (see also Figure 2) and are heat bonded to the centre of substrate materials A-C (100x110x1 mm). The felt bonding was conducted for various times at 155 °C, if not stated otherwise, and an applied pressure of 2.2kg/cm .
- the effect of felt bonding time on conductivity of the bipolar electrodes with different substrate materials are shown in Figure 6.
- Test I Area resistivity characterisation of the produced electrodes was done by means of setting the bipolar electrodes between two copper plates and applying a pressure of 0.2 kg cm " . The potential drop was measured at various currents applied to the copper plates and the resistance calculated.
- Test II Permeability, static: The bipolar electrode was assembled within two electrolyte compartments containing on the one side a 2 molar Vanadium solution comprising 1M V(III) + 1M V(IV) + 2.5M H 2 SO 4 (SOC 3.5) and on the other side of the graphite felt area a 2 molar H 2 SO 4 solution. Permeation of the Vanadium solution through the electrode at the graphite felt area was tested by means of UV-Vis analysis of the H 2 SO 4 solution.
- Test III Permeability, dynamic: The bipolar electrode was assembled in a flow cell, where on the one side a 2 molar Vanadium solution (SOC 3.5) and on the other side of the graphite felt area a 2 molar H 2 SO 4 solution were pumped through (see also Figure 3). Permeation of the Vanadium solution through the electrode at the graphite felt area was tested by means of UV-Vis analysis of the H 2 SO 4 solution.
- SOC 3.5 2 molar Vanadium solution
- H 2 SO 4 solution 2 molar H 2 SO 4 solution
- Test IV Overcharging behaviour: The bipolar electrode was overcharged for various periods at 40 mAcm " . Area resistivity before (R start ) and after overcharging (R 0 c) was measured according to Test I. Furthermore, the resistivity of the electrodes was measured after setting up the cell in a reverse mode (R rev ). This test is made to show if the oxidation products formed on the graphite felt during overcharging can be reduced and a recovering of the electrode performance is possible. Results are shown in Table III.
- Test V Cell performance: The bipolar electrode was cycled between 800 and 1800 mV Cell Voltage at 40 mAcm " . Cell Voltage was recorded with a xt-chart- recorder. Results are shown in Table IV. General cell assembly for Tests IV and V is illustrated in the scheme in Figure 4.
- the cell stack consists of two end-electrodes (glassy carbon sheets on copper current collectors), the bipolar test electrode on the positive half cell, a graphite felt in the negative half cell, a Nafion 112 membrane between the test electrode and the negative graphite felt, two flow-frames and rubber gaskets.
- Electrodes of type la ⁇ o were used for permeability tests (Test II and III) which showed no permeability of Vanadium electrolyte during 3 months for Test II and 3 weeks for Test III (Experiment was stopped after this period). The set up for permeability Test III is illustrated in Figure 3. Electrodes of type la were also used for overcharging experiments according to Test IV.
- the carbon black free bipolar electrodes of the invention showed only a i s small increase of resistance after overcharging (Roc) and reversibility of the overcharging products after reverse set up (R rev ). Results are shown in Table III. Furthermore, the la electrodes were used for evaluation of cell performance described under Test V. These results are illustrated in Table IV. Cross sections of electrodes of type la were investigated by field emission electron microscopy (FESEM). The scheme
- Example 5 Material A was used as a substrate in the above described felt bonding process I. Felt bonding time was 10 minutes. Additionally, two copper plates (LxWxH: 50x50x1 mm) were inserted on each side of the graphite felt/substrate assembly during the felt bonding process to increase the pressure on the felt for enhanced penetration of the graphite fibres into the polymer sheet substrate (see Scheme in Figure 2b). The results of the area resistivity measurements (Test I) are shown in Table II.
- Examples 6a-6b Material C was used as a substrate in the above described felt bonding process I.
- Felt bonding time was 10 minutes.
- Temperature at felt-bonding was 145°C for sample 6a and 180°C for sample 6b, respectively.
- two copper plates (LxWxH: 50x50x1 mm) were inserted on each side of the graphite felt/ substrate assembly during the felt bonding process to increase the pressure on the felt for enhanced penetration of the graphite fibres into the polymer sheet substrate (see Figure 2b).
- the results of the area resistivity measurements (Test I) are shown in Table II. Examples 7a-b
- Material C in the dimension of a full sized electrode was used as a substrate in the above described felt bonding process I.
- Felt size was 500x320x5 mm of Sigri graphite felt.
- Felt bonding time was 15 minutes for electrode 7a and 30 minutes for electrode 7b.
- Temperature at felt-bonding was 180°C.
- two copper plates (LxWxH: 500x300x1 mm) were inserted on each side of the graphite felt/substrate assembly during the felt bonding process to increase the pressure on the felt for enhanced penetration of the graphite fibres into the polymer sheet substrate (see Figure 2b).
- the results of the area resistivity measurements (Test I) are shown in Table II.
- a short length (approximately 10cm) of graphite fibre bundles in incorporated into one side of the bipolar electrode by inserting one end between the plastic sheet and graphite felt sheet, with the other end extending out past the plastic frame.
- the fibre bundle becomes embedded in the plastic sheet, but makes electrical contact with the graphite felt layer at one end, the other end remaining exposed for electrical contact outside the final stack assembly.
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00910429A EP1177590A1 (en) | 1999-03-23 | 2000-03-23 | Electrodes |
NZ514335A NZ514335A (en) | 1999-03-23 | 2000-03-23 | Bipolar composite electrodes for use in electrochemical and redox cells, characterised by an electrochemically active layer bonded to a non-conductive substrate material |
US09/937,161 US6656639B1 (en) | 1999-03-23 | 2000-03-23 | Bipolar electrode having non-conductive electrode substrate and fibrous electrochemically active material |
CA002367286A CA2367286A1 (en) | 1999-03-23 | 2000-03-23 | Electrodes |
JP2000607295A JP2002540570A (en) | 1999-03-23 | 2000-03-23 | Electrode |
AU32647/00A AU765234B2 (en) | 1999-03-23 | 2000-03-23 | Electrodes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPP9387A AUPP938799A0 (en) | 1999-03-23 | 1999-03-23 | Electrodes |
AUPP9387 | 1999-03-23 |
Publications (1)
Publication Number | Publication Date |
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WO2000057507A1 true WO2000057507A1 (en) | 2000-09-28 |
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ID=3813583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/AU2000/000241 WO2000057507A1 (en) | 1999-03-23 | 2000-03-23 | Electrodes |
Country Status (8)
Country | Link |
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US (1) | US6656639B1 (en) |
EP (1) | EP1177590A1 (en) |
JP (1) | JP2002540570A (en) |
AU (1) | AUPP938799A0 (en) |
CA (1) | CA2367286A1 (en) |
NZ (1) | NZ514335A (en) |
WO (1) | WO2000057507A1 (en) |
ZA (1) | ZA200108646B (en) |
Cited By (6)
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AT410268B (en) * | 2001-07-02 | 2003-03-25 | Funktionswerkstoffe Forschungs | LOADING OR DISCHARGE STATION FOR A REDOX FLOW BATTERY |
WO2003092138A2 (en) * | 2002-04-23 | 2003-11-06 | Unisearch Limited | Improved vanadium bromide battery (metal halide redox flow cell) |
EP1415357A1 (en) * | 2001-08-10 | 2004-05-06 | Eda, Inc. | Mixed electrolyte battery |
AT412597B (en) * | 2003-10-17 | 2005-04-25 | Funktionswerkstoffe Forschungs | ELECTRODE ARRANGEMENT OF A REDOX FLOW BATTERY |
US7976974B2 (en) | 2003-03-14 | 2011-07-12 | Newsouth Innovations Pty Limited | Vanadium halide redox flow battery |
EP3111495A4 (en) * | 2014-02-26 | 2017-09-27 | Redflow R & D Pty Ltd. | Bipolar battery electrode having improved carbon surfaces and method of manufacturing same |
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EP1561253A2 (en) * | 2002-09-30 | 2005-08-10 | E.I. Du Pont De Nemours And Company | Method for regeneration of performance in a fuel cell |
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KR20210066649A (en) | 2019-11-28 | 2021-06-07 | 지엔에스티주식회사 | Separator for Redox Flow Battery and Manufacturing Method Thereof |
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- 2000-03-23 US US09/937,161 patent/US6656639B1/en not_active Expired - Fee Related
- 2000-03-23 NZ NZ514335A patent/NZ514335A/en unknown
- 2000-03-23 CA CA002367286A patent/CA2367286A1/en not_active Abandoned
- 2000-03-23 WO PCT/AU2000/000241 patent/WO2000057507A1/en not_active Application Discontinuation
- 2000-03-23 EP EP00910429A patent/EP1177590A1/en not_active Withdrawn
- 2000-03-23 JP JP2000607295A patent/JP2002540570A/en active Pending
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- 2001-10-19 ZA ZA200108646A patent/ZA200108646B/en unknown
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JPS63164169A (en) * | 1986-12-25 | 1988-07-07 | Nippon Steel Chem Co Ltd | Manufacture of conductive plastic electrode |
JPS63281359A (en) * | 1987-05-12 | 1988-11-17 | Nippon Steel Chem Co Ltd | Manufacture of conductive plastic electrode |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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AT410268B (en) * | 2001-07-02 | 2003-03-25 | Funktionswerkstoffe Forschungs | LOADING OR DISCHARGE STATION FOR A REDOX FLOW BATTERY |
EP1415357A1 (en) * | 2001-08-10 | 2004-05-06 | Eda, Inc. | Mixed electrolyte battery |
EP1415354A1 (en) * | 2001-08-10 | 2004-05-06 | Eda, Inc. | Cerium batteries |
EP1415358A2 (en) * | 2001-08-10 | 2004-05-06 | Eda, Inc. | Secondary battery with autolytic dendrites |
EP1415354A4 (en) * | 2001-08-10 | 2006-08-02 | Eda Inc | Cerium batteries |
EP1415358A4 (en) * | 2001-08-10 | 2006-08-09 | Eda Inc | Secondary battery with autolytic dendrites |
EP1415357A4 (en) * | 2001-08-10 | 2007-05-02 | Eda Inc | Mixed electrolyte battery |
WO2003092138A2 (en) * | 2002-04-23 | 2003-11-06 | Unisearch Limited | Improved vanadium bromide battery (metal halide redox flow cell) |
WO2003092138A3 (en) * | 2002-04-23 | 2004-03-04 | Fuel Technology Ltd E | Improved vanadium bromide battery (metal halide redox flow cell) |
US7976974B2 (en) | 2003-03-14 | 2011-07-12 | Newsouth Innovations Pty Limited | Vanadium halide redox flow battery |
AT412597B (en) * | 2003-10-17 | 2005-04-25 | Funktionswerkstoffe Forschungs | ELECTRODE ARRANGEMENT OF A REDOX FLOW BATTERY |
EP3111495A4 (en) * | 2014-02-26 | 2017-09-27 | Redflow R & D Pty Ltd. | Bipolar battery electrode having improved carbon surfaces and method of manufacturing same |
Also Published As
Publication number | Publication date |
---|---|
JP2002540570A (en) | 2002-11-26 |
ZA200108646B (en) | 2003-02-26 |
NZ514335A (en) | 2002-08-28 |
AUPP938799A0 (en) | 1999-04-15 |
CA2367286A1 (en) | 2000-09-28 |
US6656639B1 (en) | 2003-12-02 |
EP1177590A1 (en) | 2002-02-06 |
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